DE68910411T2 - Oxidation hydrolysis of iodoalkanes. - Google Patents
Oxidation hydrolysis of iodoalkanes.Info
- Publication number
- DE68910411T2 DE68910411T2 DE68910411T DE68910411T DE68910411T2 DE 68910411 T2 DE68910411 T2 DE 68910411T2 DE 68910411 T DE68910411 T DE 68910411T DE 68910411 T DE68910411 T DE 68910411T DE 68910411 T2 DE68910411 T2 DE 68910411T2
- Authority
- DE
- Germany
- Prior art keywords
- iodine
- reaction
- iodoalkanes
- iodoalkane
- iodomethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 230000007062 hydrolysis Effects 0.000 title description 6
- 238000006460 hydrolysis reaction Methods 0.000 title description 6
- 230000003647 oxidation Effects 0.000 title description 6
- 238000007254 oxidation reaction Methods 0.000 title description 6
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 30
- 239000011630 iodine Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 claims description 12
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000000243 solution Substances 0.000 description 7
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 3
- 238000006400 oxidative hydrolysis reaction Methods 0.000 description 3
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229940107816 ammonium iodide Drugs 0.000 description 2
- 239000012736 aqueous medium Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- FMKOJHQHASLBPH-UHFFFAOYSA-N isopropyl iodide Chemical compound CC(C)I FMKOJHQHASLBPH-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- IQRUSQUYPCHEKN-UHFFFAOYSA-N 2-iodobutane Chemical compound CCC(C)I IQRUSQUYPCHEKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WAIPAZQMEIHHTJ-UHFFFAOYSA-N [Cr].[Co] Chemical compound [Cr].[Co] WAIPAZQMEIHHTJ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-BJUDXGSMSA-N iodomethane Chemical group I[11CH3] INQOMBQAUSQDDS-BJUDXGSMSA-N 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/12—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids
- C07C29/124—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of mineral acids of halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/13—Iodine; Hydrogen iodide
- C01B7/14—Iodine
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Diese Erfindung betrifft die Oxidationshydrolyse von Iodoalkanen, bei der ein Alkanol und elementares Iod durch Kontaktieren eines Iodoalkans, Wasser und molekularem Sauerstoff erzeugt werden. Da das Iod in elementarer Form vorliegt, läßt es sich leicht gewinnen.This invention relates to the oxidation hydrolysis of iodoalkanes, in which an alkanol and elemental iodine are produced by contacting an iodoalkane, water and molecular oxygen. Since the iodine is in elemental form, it is easily recovered.
Es sind eine Anzahl von Verfahren entwickelt worden, um Iodwerte aus anorganischen Iod enthaltenden Verbindungen zu gewinnen. Beispielsweise wird Iod im technischen Maßstab aus Tiefbrunnensole durch Chloroxidation gewonnen. Iodwerte lassen sich auch durch Oxidation von sauren Solen mit Cuprisulfat oder Ferrisulfat gewinnen. Alternativ kann eine Elektrolyse von Ammoniumiodidlösungen durchgeführt werden, wie es in der U.S.- Patentschrift 3,975,439 beschrieben wird. Die katalytische Oxidation von Ammoniumiodidlösungen durch Sauerstoff in Gegenwart von Kupferkatalysatoren wird in der japanischen Patentanmeldung Kokai Nr. 73489/1978 beschrieben. In jüngerer Zeit wurde in der EP 0218998 ein Verfahren zur Gewinnung von elementarem Iod aus wäßrigem Natriumiodid oder einer Mischung von Iodobenzol und NaI beschrieben, und zwar durch Ansäuern mit Kohlendioxid und Oxidation mit molekularem Sauerstoff. Diese Verfahren ermöglichen jedoch nicht die Gewinnung von elementarem Iod aus Iodoalkanen oder substituierten Iodoalkanen. In der U.S.-Patentschrift 4,085,200 wird ein Verfahren zur thermochemischen Erzeugung von Methan und Sauerstoff aus Wasser und Kohlendioxid beschrieben, bei dem als Zwischenstufe die Hydrolyse von Iodomethan zu Methanol, Dimethylether und waßrigem HI durchgeführt wird; dies Verfahren ermöglicht jedoch nicht die Produktion von elementarem Iod oder von einem Alkanol. Eine einfache Hydrolyse von Iodoalkanen durch Wasser führt im PrinziP zu Alkanol und wäßriger Iodwasserstoffsäure; dies ermöglicht jedoch nicht die Durchführung eines vom kommerziellen Standpunkt aus gesehen geeigneten Verfahrens, da das Reaktions- Gleichgewicht A number of processes have been developed to recover iodine values from inorganic iodine-containing compounds. For example, iodine is recovered on an industrial scale from deep well brine by chlorine oxidation. Iodine values can also be recovered by oxidation of acidic brines with cupric sulfate or ferric sulfate. Alternatively, electrolysis of ammonium iodide solutions can be carried out as described in US Patent 3,975,439. The catalytic oxidation of ammonium iodide solutions by oxygen in the presence of copper catalysts is described in Japanese Patent Application Kokai No. 73489/1978. More recently, EP 0218998 describes a process for recovering elemental iodine from aqueous sodium iodide or a mixture of iodobenzene and NaI by acidification with carbon dioxide and oxidation with molecular oxygen. However, these processes do not enable the recovery of elemental iodine from iodoalkanes or substituted iodoalkanes. US Patent 4,085,200 describes a process for the thermochemical production of methane and oxygen from water and carbon dioxide, in which the intermediate step is the hydrolysis of iodomethane to methanol, dimethyl ether and aqueous HI; however, this process does not allow the production of elemental iodine or an alkanol. A simple hydrolysis of iodoalkanes by water leads in principle to alkanol and aqueous hydriodic acid; however, this does not allow the implementation of a process suitable from a commercial point of view, since the reaction equilibrium
weit links liegt, wodurch die Umwandlung auf einige wenige Prozent begrenzt wird. Weiterhin ist die Gewinnung von konzentriertem HI aus dem verdünnten wäßrigen Medium sehr kostspielig.lies far to the left, limiting the conversion to a few percent. Furthermore, the recovery of concentrated HI from the dilute aqueous medium is very costly.
Es wurde nun gefunden, daß die lodwerte in Iodoalkanen leicht in ökonomischer Weise gewonnen werden können, indem man eine oxidative Hydrolyse in flüssiger Phase durchführt, wobei die Hydrolyse des Iodoalkans in Gegenwart von molekularem Sauerstoff und Wasser bei einer TemPeratur von über 100ºC erfolgt. Unter diesen Bedingungen wird das durch Hydrolyse freigesetzte HI schnell zu elementarem Iod oxidiert. Die Gesamt-Reaktion ist demnach wie folgt:It has now been found that the iodine values in iodoalkanes can be easily recovered economically by carrying out an oxidative hydrolysis in the liquid phase, whereby the hydrolysis of the iodoalkane takes place in the presence of molecular oxygen and water at a temperature of over 100ºC. Under these conditions, the HI released by hydrolysis is quickly oxidized to elemental iodine. The overall reaction is therefore as follows:
R-I + 1/2 H&sub2;O + 1/4 O&sub2; T ROH + 1/2 I&sub2;.R-I + 1/2 H₂O + 1/4 O₂ T ROH + 1/2 I₂.
Das in diesem Verfahren erzeugte Iod ist in dem wäßrigen Medium relativ unlöslich und läßt sich leicht durch eine Vielzahl von Verfahren gewinnen, einschließlich Dekantieren, wenn das Iod geschmolzen ist, Filtrieren, wenn das Iod durch Abkühlen verfestigt ist oder durch Extrahieren mit einem Kohlenwasserstofflösungsmittel. Die Alkanolwerte können aus der wäßrigen Lösung auch durch Destillation entfernt werden, und zwar im Falle von niedrigsiedenden Alkanolen, wie z. B. Methanol oder Ethanol oder durch Extraktion im Falle von höhersiedenden, weniger hydrophilen Alkanolen.The iodine produced in this process is relatively insoluble in the aqueous medium and is readily recovered by a variety of methods, including decantation if the iodine is molten, filtration if the iodine is solidified by cooling, or extraction with a hydrocarbon solvent. The alkanol values can also be removed from the aqueous solution by distillation in the case of lower boiling alkanols such as methanol or ethanol or by extraction in the case of higher boiling, less hydrophilic alkanols.
Die Iodoalkane, die bei diesem Verfahren verwendet werden können, enthalten 1 - 20 Kohlenstoffatome, wobei zu ihnen primäre, sekundäre und tertiäre Iodoalkane gehören. Vorzugsweise ist das Iodoalkan ein sekundäres oder primäres Iodoalkan mit 1 - 5 Kohlenstoffatomen. Zu geeigneten Iodoalkanen gehören Iodomethan, Iodoethan, 1-Iodopropan, 2-Iodopropan, 1-Iodobutan und 2-Iodobutan. Besonders vorteilhaft ist ein primäres Iodoalkan mit 1 - 3 Kohlenstoffatomen, wie z. B. Iodomethan und Iodoethan. Das am meisten bevorzugte Iodoalkan ist Iodomethan.The iodoalkanes that can be used in this process contain 1-20 carbon atoms and include primary, secondary and tertiary iodoalkanes. Preferably, the iodoalkane is a secondary or primary iodoalkane having 1-5 carbon atoms. Suitable iodoalkanes include iodomethane, iodoethane, 1-iodopropane, 2-iodopropane, 1-iodobutane and 2-Iodobutane. Particularly advantageous is a primary iodoalkane with 1 - 3 carbon atoms, such as iodomethane and iodoethane. The most preferred iodoalkane is iodomethane.
Die Umsetzung erfolgt bei Temperaturen von 50ºC - 250ºC. Bei niedrigeren Temperaturen wird die Reaktionsgeschwindigkeit in nicht akzeptierbarer Weise gering, wohingegen bei den höheren Temperaturen der Reaktionsdruck in nicht akzeptierbarer Weise hoch wird. Dies bedeutet, daß praktische Reaktionstemperaturen bei 100ºC - 200ºC liegen, vorzugsweise bei Temperaturen im Bereich von 125ºC - 175ºC.The reaction takes place at temperatures of 50ºC - 250ºC. At lower temperatures the reaction rate becomes unacceptably low, whereas at higher temperatures the reaction pressure becomes unacceptably high. This means that practical reaction temperatures are 100ºC - 200ºC, preferably at temperatures in the range of 125ºC - 175ºC.
Der molekulare Sauerstoff kann der Reaktion in jeder geeigneten Form zugeführt werden, einschließlich in Form von Luft, in Form von angereicherter Luft, in Form von reinem Sauerstoff und in Form von erschöpfter Luft.The molecular oxygen can be supplied to the reaction in any suitable form, including air, enriched air, pure oxygen and depleted air.
Der Druck des zugeführten Sauerstoffs kann variieren von unteratmosphärischem bis überatmosphärischem Druck, wobei überatmosphärische Drucke bevorzugt sind. Bevorzugte Gesamtdrucke liegen bei 1 - 105 kg/cm², wobei der bevorzugten Bereich bei 7 - 70,3 kg/cm² liegt. Der Reaktionsdruck muß ausreichend sein, so daß eine wäßrige Phase im Reaktor aufrechterhalten wird.The pressure of the oxygen supplied can vary from subatmospheric to superatmospheric pressure, with superatmospheric pressures being preferred. Preferred total pressures are 1 - 105 kg/cm², with the preferred range being 7 - 70.3 kg/cm². The reaction pressure must be sufficient so that an aqueous phase is maintained in the reactor.
Die Reaktion kann entweder kontinuierlich oder chargenweise durchgeführt werden. Im Falle einer Verfahrensweise im großen Maßstab ist eine kontinuierliche Verfahrensweise vorzuziehen, während ein chargenweises Verfahren bei Verfahren in kleinerem Maßstabe vorteilhaft sein kann.The reaction can be carried out either continuously or batchwise. In case of large-scale operation, a continuous operation is preferable, while a batchwise operation may be advantageous in smaller-scale operations.
Die Reaktionsdauer hängt von der Reaktionstemperatur und dem Druck ab, liegt im allgemeinen jedoch zwischen 10 Stunden und 10 Minuten. Höhere Temperaturen und höhere Drucke begünstigen kürzere Reaktionszeiten.The reaction time depends on the reaction temperature and pressure, but is generally between 10 hours and 10 minutes. Higher temperatures and higher pressures favor shorter reaction times.
Beim Verfahren dieser Erfindung ist kein Katalysator erforderlich. Dies vereinfacht die Verfahrensdurchführung, da keine Anlage zur Katalysatorentfernung erforderlich ist und da keine zusätzlichen Kosten bezüglich der Verwendung eines Katalysators auftreten.The process of this invention does not require a catalyst. This simplifies the process because no A catalyst removal system is required and there are no additional costs associated with using a catalyst.
Die folgenden Beispiele veranschaulichen das Verfahren der vorliegenden Erfindung. In jedem Beispiel wurden die angegebenen Reaktionskomponenten in einen 330 mL fassenden Autoklaven vom Typ Hastelloy C gegeben, in dem sie den angegebenen Reaktionsbedingungen und Zeiten unterworfen wurden. Die Reaktionsprodukte wurder dann entfernt und analysiert. Alle Prozentangaben sind in Gew.-%.The following examples illustrate the process of the present invention. In each example, the indicated reaction components were placed in a 330 mL Hastelloy C autoclave and subjected to the indicated reaction conditions and times. The reaction products were then removed and analyzed. All percentages are in weight percent.
100 mL H&sub2;O100 mL H₂O
10 mL Iodomethan10 mL iodomethane
120ºC120ºC
14,0 kg/cm² Luft14.0 kg/cm² air
1 Stunde.1 hour.
Bei der Reaktion wurde sämtlicher zur Verfügung stehender Sauerstoff verbraucht. Die Reaktions1ösung enthielt 81,82 % H&sub2;O, 3,85 % Methanol und 12 % Iod sowie 0,0 % Iodomethan. Zusätzlich wurden mehrere Gramm von kristallinem Iod im Autoklaven gefunden.During the reaction, all available oxygen was consumed. The reaction solution contained 81.82% H₂O, 3.85% methanol and 12% iodine as well as 0.0% iodomethane. In addition, several grams of crystalline iodine were found in the autoclave.
100 mL H&sub2;O100 mL H₂O
10 mL Iodomethan10 mL iodomethane
150ºC150ºC
28,1 kg/cm² Luft28.1 kg/cm² air
1 Stunde.1 hour.
Im Verlaufe der Reaktion trat ein Druckabfall von 7 kg/cm² innerhalb von 30 Minuten auf. Die Reaktionslösung enthielt 89,7 % Wasser, 3,71 % Methanol, 3,78 % Iod und 0,0 % Iodomethan.During the course of the reaction, a pressure drop of 7 kg/cm² occurred within 30 minutes. The reaction solution contained 89.7% water, 3.71% methanol, 3.78% iodine and 0.0% iodomethane.
Zusätzlich wurden im Autoklaven 15 g kristallines Iod gefunden. Dieses Beispiel zeigt die hohe Reaktionsgeschwindigkeit für die oxidative Hydrolysenreaktion bei 150ºC.Additionally, 15 g of crystalline iodine were found in the autoclave. This example shows the high reaction rate for the oxidative hydrolysis reaction at 150ºC.
100 mL H&sub2;O100 mL H₂O
10 mL Iodomethan10 mL iodomethane
100ºC100ºC
28,1 kg/cm² Luft28.1 kg/cm² air
1 Stunde.1 hour.
Die Reaktionslösung enthielt 95,1 % Wasser, 1,15 % Methanol, 1,1 % Iod und 0,7 % Iodomethan. Zusätzlich wurde flüssiges Iodomethan in Form einer zweiten Schicht festgestellt. Es hatte sich kein kristallines Iod gebildet. Dieses Beispiel zeigt die geringere Reaktionsgeschwindigkeit für die oxidative Hydrolysenreaktion bei 100ºC.The reaction solution contained 95.1% water, 1.15% methanol, 1.1% iodine and 0.7% iodomethane. In addition, liquid iodomethane was found in the form of a second layer. No crystalline iodine had formed. This example shows the lower reaction rate for the oxidative hydrolysis reaction at 100ºC.
100 mL H&sub2;O100 mL H₂O
10 mL Iodoethan10 mL iodoethane
120ºC120ºC
28,1 kg/cm² Luft28.1 kg/cm² air
2 Stunden.2 hours.
Der Reaktionsdruck fiel innerhalb eines Zeitraumes von 1 Stunde um 6,6 kg/cm² ab. Die Reaktionslösung enthielt 12,3 % Ethanol, 4,5 % Diethylether, 5,3 % Iod und 76,1 % H&sub2;O. Zusätzlich wurden in dem Autoklaven 10,1 g kristallines Iod gefunden.The reaction pressure dropped by 6.6 kg/cm² within a period of 1 hour. The reaction solution contained 12.3% ethanol, 4.5% diethyl ether, 5.3% iodine and 76.1% H₂O. In addition, 10.1 g of crystalline iodine were found in the autoclave.
100 mL H&sub2;O100 mL H₂O
10 mL 2-Iodopropan10 mL 2-iodopropane
120ºC120ºC
28,1 kg/cm² Luft28.1 kg/cm² air
2 Stunden.2 hours.
Der Reaktionsdruck fiel um 5,3 kg/cm² Innerhalb eines Zeitraumes von 1 Stunde. Die Reaktionslösung enthielt 13,2 % 2-Propanol, 6,2 % Iod und 78,3 % Wasser. Zusätzlich wurden im Autoklaven 3,4 g kristallines Iod gefunden.The reaction pressure dropped by 5.3 kg/cm2 within a period of 1 hour. The reaction solution contained 13.2% 2-propanol, 6.2% iodine and 78.3% water. In addition, 3.4 g of crystalline iodine were found in the autoclave.
Claims (3)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/220,844 US4863710A (en) | 1988-07-15 | 1988-07-15 | Oxidation hydrolysis of iodoalkanes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE68910411D1 DE68910411D1 (en) | 1993-12-09 |
| DE68910411T2 true DE68910411T2 (en) | 1994-06-01 |
Family
ID=22825218
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE68910411T Expired - Fee Related DE68910411T2 (en) | 1988-07-15 | 1989-07-13 | Oxidation hydrolysis of iodoalkanes. |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4863710A (en) |
| EP (2) | EP0351338B1 (en) |
| JP (1) | JPH04500496A (en) |
| KR (1) | KR970000891B1 (en) |
| AT (1) | ATE96761T1 (en) |
| CA (1) | CA1320037C (en) |
| DE (1) | DE68910411T2 (en) |
| ES (1) | ES2045522T3 (en) |
| WO (1) | WO1990000520A1 (en) |
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| US7010961B2 (en) * | 2002-09-10 | 2006-03-14 | Gilbarco Inc. | Power head secondary containment leak prevention and detection system and method |
| US7251983B2 (en) * | 2002-09-10 | 2007-08-07 | Gilbarco Inc. | Secondary containment system and method |
| US6978661B2 (en) * | 2002-09-10 | 2005-12-27 | Gilbarco Inc. | Secondary containment leak prevention and detection system and method in fuel dispenser |
| US6997042B2 (en) * | 2002-09-10 | 2006-02-14 | Gilbarco Inc. | Secondary containment leak prevention and detection system and method |
| US6834534B2 (en) * | 2003-03-17 | 2004-12-28 | Veeder-Root Company | Fuel storage tank leak prevention and detection system and method |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1849844A (en) * | 1926-02-06 | 1932-03-15 | Lloyd Stewart Joseph | Method for hydrolyzing the halides of hydrocarbons and their derivatives |
| US1936553A (en) * | 1932-01-18 | 1933-11-21 | Jones Chemical Company Inc | Preparation of pure iodine |
| US3006731A (en) * | 1957-10-29 | 1961-10-31 | Shell Oil Co | Process for the recovery of iodine |
| GB887678A (en) * | 1959-07-16 | 1962-01-24 | Distillers Co Yeast Ltd | Production of aliphatic alcohols |
| US3425798A (en) * | 1966-01-10 | 1969-02-04 | Eastman Kodak Co | Process for the removal of iodine from organic compounds |
| US3839547A (en) * | 1972-12-01 | 1974-10-01 | Gulf Research Development Co | Process for recovering hbr and bromine from 2,3,3-tribromo-2-alkylalkanes |
| US3975439A (en) * | 1973-07-26 | 1976-08-17 | E. I. Du Pont De Nemours And Company | Preparation and amination of iodoaniline |
| DE2606886A1 (en) * | 1976-02-20 | 1977-09-01 | Rheinische Braunkohlenw Ag | THERMOCHEMICAL PROCESS FOR GENERATING METHANE FROM CARBON DIOXIDE AND WATER |
| JPS5373489A (en) * | 1976-12-14 | 1978-06-29 | Teijin Ltd | Production of iodine |
| IT1207506B (en) * | 1985-10-15 | 1989-05-25 | Montedipe Spa | PROCESS FOR THE RECOVERY OF THE IODINE FROM THE SODIUM IODIDE. |
-
1988
- 1988-07-15 US US07/220,844 patent/US4863710A/en not_active Expired - Fee Related
-
1989
- 1989-07-11 CA CA000605292A patent/CA1320037C/en not_active Expired - Fee Related
- 1989-07-13 JP JP1508222A patent/JPH04500496A/en active Pending
- 1989-07-13 EP EP89420254A patent/EP0351338B1/en not_active Expired - Lifetime
- 1989-07-13 AT AT89420254T patent/ATE96761T1/en not_active IP Right Cessation
- 1989-07-13 ES ES89420254T patent/ES2045522T3/en not_active Expired - Lifetime
- 1989-07-13 KR KR1019900700552A patent/KR970000891B1/en active IP Right Grant
- 1989-07-13 EP EP89908746A patent/EP0425570A1/en active Pending
- 1989-07-13 DE DE68910411T patent/DE68910411T2/en not_active Expired - Fee Related
- 1989-07-13 WO PCT/US1989/003027 patent/WO1990000520A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| US4863710A (en) | 1989-09-05 |
| CA1320037C (en) | 1993-07-13 |
| JPH04500496A (en) | 1992-01-30 |
| KR900701648A (en) | 1990-12-04 |
| ES2045522T3 (en) | 1994-01-16 |
| EP0425570A1 (en) | 1991-05-08 |
| ATE96761T1 (en) | 1993-11-15 |
| EP0351338B1 (en) | 1993-11-03 |
| EP0351338A1 (en) | 1990-01-17 |
| KR970000891B1 (en) | 1997-01-21 |
| WO1990000520A1 (en) | 1990-01-25 |
| DE68910411D1 (en) | 1993-12-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8364 | No opposition during term of opposition | ||
| 8327 | Change in the person/name/address of the patent owner |
Owner name: EASTMAN CHEMICAL CO., KINGSPORT, TENN., US |
|
| 8339 | Ceased/non-payment of the annual fee |